JP4345064B2 - Method for manufacturing photoelectric conversion element and electronic device - Google Patents

Description

  The present invention relates to a method for producing a photoelectric conversion element using a liquid containing a silicon compound, and an electronic device including the photoelectric conversion element produced by the method.

  Conventionally, photoelectric conversion elements such as solar cells have attracted attention as environmentally friendly power sources, and single-crystal silicon type solar cells used for power sources for satellites, etc., and solar cells using polycrystalline silicon or amorphous silicon Are widely used for industrial and household purposes.

  In general, an amorphous silicon solar cell has a so-called PIN structure in which a first conductive semiconductor layer and a second conductive semiconductor layer (for example, a P-type semiconductor layer and an N-type semiconductor layer) sandwich a light absorption layer made of an I-type semiconductor layer. A photocurrent and a photovoltaic force are extracted from the electrode by using a built-in electric field that has a structure called and can be formed in the I-type semiconductor layer.

In International Publication No. WO00 / 59044, as a method for producing a solar cell at a low cost without using large-scale equipment, a coating composition is formed by applying a liquid coating composition containing a silicon compound on a substrate, There has been proposed a method of using a silicon film formed by heat treatment and / or light treatment of a coating film as a semiconductor layer.
International Publication No. WO00 / 59044

  A method of applying a liquid coating composition containing a silicon compound on a substrate can form a thin film having a thickness of 200 to 300 nm. However, if a film having a thickness larger than that is formed, cracks may occur. It is known that it will peel off from the substrate.

  However, in a solar cell having a PIN structure, it is desirable that the thickness of the I layer be about 2 μm in order to obtain high photoelectric conversion efficiency. Therefore, a method of applying the coating composition on the substrate is not suitable, and it is generally formed by a relatively expensive method such as a CVD method.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a micron-order I-type semiconductor layer required for a PIN structure solar cell using a liquid silicon material at a low cost.

In order to solve the above problems, a method for manufacturing a photoelectric conversion element of the present invention includes a step of forming a first electrode on a substrate, and a step of forming a first conductive semiconductor layer on the first electrode. Forming an I-type semiconductor layer on the first conductive semiconductor layer, forming a second conductive semiconductor layer different from the first conductive type on the I-type semiconductor layer, and the second Forming a second electrode on the conductive type semiconductor layer, wherein the step of forming the I type semiconductor layer forms a droplet containing a silicon compound on the first conductive type semiconductor layer in an island shape. Forming a precursor film of the I-type semiconductor layer, and performing a heat treatment or a light irradiation process on the precursor film to convert the precursor film into the I-type semiconductor layer; The I-type semiconductor layer disposed in the island shape is formed on the first conductive type semiconductor layer. The area without, characterized in that it comprises a, placing a droplet containing the silicon compound.
In addition, the manufacturing method of the said photoelectric conversion element respond | corresponds to 2nd Embodiment demonstrated in this specification.

When a liquid containing a silicon compound is arranged as an approximately hemispherical droplet in an island shape on the first semiconductor layer, the film is thicker than when a coating film is formed over a large area by spin coating or the like. Can be formed. Although the thickness of the substantially hemispherical droplet is reduced by the influence of the solvent and hydrogen being removed in the subsequent heating or light irradiation process, it is possible to obtain a micron-order semiconductor thin film. In such a semiconductor thin film, it is difficult for cracks to occur, and it is difficult to peel off from the substrate.
In addition, according to the present invention, a sufficiently thick I-type semiconductor layer suitable for a solar cell can be formed on the entire surface of the first conductivity type semiconductor layer.

  Further, before the step of forming the second semiconductor layer, a liquid repellent film is formed in a region on the first semiconductor layer other than the region where the droplets containing the silicon compound are to be disposed. Preferably, the method further includes the step of:

  If a lyophobic / lyophilic pattern is formed on the surface of the first semiconductor layer before placing a droplet containing a silicon compound, the droplet remains in the lyophilic region and becomes lyophobic. It will not spread over the area. As a result, more droplets can be arranged in the lyophilic region, and the thickness of the droplets can be increased.

  In addition, after the heat treatment or light irradiation treatment step, the thickness of the silicon film is preferably 1 μm or more. By setting the film thickness of the I-type semiconductor layer to 1 μm or more, preferably 2 μm or more, a photoelectric conversion element with high photoelectric conversion efficiency and high performance can be obtained.

  Moreover, it is preferable to adjust so that the contact angle with respect to the said liquid repellent film | membrane of the droplet containing a silicon compound may be set to 40 degree | times -120 degree | times. By controlling the contact angle to be within this range, it is possible to dispose a thick and well-shaped droplet. The contact angle can be controlled by appropriately selecting the material of the first semiconductor layer, the solvent of the droplet containing the silicon compound, the liquid repellent film, and the like. When the contact angle is 40 degrees or less, sufficient droplets cannot be disposed in the lyophilic region, and it becomes difficult to obtain a silicon film having a required film thickness. In addition, when the contact angle is 120 or more, the adhesion may be weakened when the third semiconductor layer is formed.

In order to solve the above problems, the present invention also includes a step of forming a first electrode on a substrate, a step of forming a first semiconductor layer on the first electrode, and the first semiconductor. Forming an I-type second semiconductor layer on the layer, forming an N-type or P-type third semiconductor layer on the second semiconductor layer, and forming on the third semiconductor layer Forming a second electrode, wherein the third semiconductor layer is N-type when the first semiconductor layer is P-type, and the first semiconductor layer is N-type when the first semiconductor layer is N-type. 3 is a method for manufacturing a photoelectric conversion element having a P-type semiconductor layer, wherein the step of forming the first semiconductor layer comprises forming droplets containing a silicon compound on the first semiconductor layer as islands. After forming a silicon film precursor film, heat treatment or light irradiation treatment is performed to form the precursor film into silicon. A first silicon film forming step that changes into a silicon film, and a droplet containing a silicon compound is arranged in an island shape with a center shifted from the silicon film formed in the first silicon film forming step. And a second silicon film forming step of converting the precursor film into a silicon film by performing a heat treatment or a light irradiation treatment after the body film is formed.
According to such a configuration, the surface of the first semiconductor layer can be covered with a substantially hemispherical droplet containing a silicon compound, so that a photoelectric conversion element having a wider area can be formed.

  In addition, before the first silicon film formation step, the method further includes a step of forming a liquid repellent film in a region on the first semiconductor layer other than the region where the droplets containing the silicon compound are to be disposed. Is also preferable. As described above, if a lyophobic / lyophilic pattern is formed on the surface of the first semiconductor layer before placing the droplet containing the silicon compound, the droplet is placed in the lyophilic region. It stays and does not spread out in the liquid repellent area. As a result, more droplets can be arranged in the lyophilic region, and the thickness of the droplets can be increased.

  Further, before the second silicon film forming step, the method further includes a step of forming a liquid repellent film on the first semiconductor layer and the silicon film formed in the first silicon film forming step. Is preferred. As a result, the droplets disposed on the substrate and the silicon film formed in the first silicon film formation step do not spread and become spherical, and it becomes easier to form a thicker thin film.

  It is also preferable to repeat the second silicon film forming step twice or more. By repeating two or more times, an I-type semiconductor layer can be formed on the entire surface even when the silicon film cannot be formed on the entire surface of the first semiconductor layer by only one time. If a thin film can be formed once on the entire surface and then repeated further, a thicker I-type semiconductor layer can be formed.

  It is also preferable to further include a step of forming a liquid repellent film on the first semiconductor layer and the already formed silicon film before each second silicon film forming step that is repeatedly performed twice or more. Thereby, at each time, the droplet containing the silicon compound to be arranged does not spread out and it becomes easy to take a spherical form, and it becomes easy to form a thicker thin film.

  Moreover, it is preferable that the said silicon compound contains a higher order silane compound. The higher order silane compound can be arranged as droplets as it is or dissolved in an organic solvent. Then, it is converted into a silicon film by baking in an inert gas atmosphere.

  In addition, it is preferable that the droplet containing a silicon compound is arrange | positioned by the inkjet method. According to the ink jet method, minute droplets can be accurately discharged and arranged at a desired location.

  The substrate used in the method for manufacturing a photoelectric conversion element according to the present invention is preferably a flexible substrate mainly composed of a resin material. Thereby, a flexible photoelectric conversion element can be formed.

  Furthermore, this invention provides an electronic device provided with the photoelectric conversion element manufactured by the manufacturing method of the photoelectric conversion element of this invention. The electronic device according to the present invention is a high-performance device provided with a photoelectric conversion element having excellent photoelectric conversion efficiency.

  Hereinafter, a method for manufacturing a photoelectric conversion element, a photoelectric conversion element, and an electronic device of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

<First Embodiment>
FIG. 1 is a perspective view showing an embodiment of a photoelectric conversion element of the present invention. In the following description, on the paper surface in FIG. 1, the upper side is referred to as “upper” or “upper”, the lower side is referred to as “lower” or “lower”, and the upper surface of each layer (each member) is referred to as “upper surface”. The lower surface is called the “lower surface”.

  The photoelectric conversion element 1 shown in FIG. 1 is a so-called dry photoelectric conversion element that does not require an electrolyte solution. The photoelectric conversion element 1 includes a substrate 10, a first electrode (surface electrode) 12, a P-type semiconductor layer 14 as a first semiconductor layer, an I-type semiconductor layer 16 as a second semiconductor layer, It has an N-type semiconductor layer 18 as a third semiconductor layer and a second electrode (counter electrode) 20. Hereinafter, the configuration of each layer (each part) will be described.

  The substrate 10 supports each layer of the first electrode 12, the P-type semiconductor layer 14, the I-type semiconductor layer 16, the N-type semiconductor layer 18, and the second electrode 20. The substrate 10 is composed of a flat (or layered) member.

  In the photoelectric conversion element 1 of the present embodiment, as shown in FIG. 1, for example, light such as sunlight (hereinafter simply referred to as “light”) is incident from the substrate 10 and the first electrode 12 side described later. It is intended to be used (irradiated). For this reason, each of the substrate 10 and the first electrode 12 is preferably substantially transparent (colorless transparent, colored transparent, or translucent). Thereby, light can efficiently reach the I-type semiconductor layer 16.

  In FIG. 2, the manufacturing process of the photoelectric conversion element 1 is shown.

(First electrode forming step)
First, as shown in FIG. 2A, the first electrode 12 is formed over the substrate 10. Examples of the constituent material of the substrate 10 include various glass materials, various ceramic materials, various resin materials such as polycarbonate (PC) and polyethylene terephthalate (PET). Moreover, the board | substrate 10 may be comprised by the laminated body of the single layer or multiple layers. The average thickness of the substrate 10 is appropriately set depending on the material, use, and the like, and is not particularly limited. For example, the average thickness can be as follows.

  When the substrate 10 is hard, the average thickness is preferably about 0.1 to 1.5 mm, and more preferably about 0.8 to 1.2 mm. When the substrate 10 is flexible (flexible) (a flexible substrate mainly composed of a resin material), the average thickness is preferably about 0.5 to 150 μm. More preferably, it is about 10 to 75 μm.

  In addition, when mounting the photoelectric conversion element 1 in various electronic devices, the structural member of an electronic device can be utilized as the board | substrate 10 of the photoelectric conversion element 1. FIG.

A layered first electrode (surface electrode) 12 is provided on the upper surface of the substrate 10. Examples of the constituent material of the first electrode 12 include various metal oxides such as indium oxide (ITO) to which tin is added, tin oxide (FTO) doped with fluorine, indium oxide (IO), and tin oxide (SnO ₂ ). Materials (transparent conductive oxides), various metal materials such as aluminum, nickel, cobalt, platinum, silver, gold, copper, molybdenum, titanium, tantalum or alloys containing these, various types such as carbon, carbon nanotubes, fullerenes Examples thereof include carbon materials, and one or more of them can be used in combination, and a thin film electrode can be formed by a sputtering method, a spray method, a spin coating method, an ink jet method or the like.

  The average thickness of the first electrode 12 is appropriately set depending on the material, application, and the like, and is not particularly limited. For example, the average thickness can be as follows. When the first electrode 12 is composed of various metal oxides, the average thickness is preferably about 0.05 to 5 μm, and more preferably about 0.1 to 1.5 μm. Moreover, when the 1st electrode 12 is comprised with various metal materials and various carbon materials, it is preferable that the average thickness is about 0.01-1 micrometer, and it is about 0.03-0.1 micrometer. More preferred.

(P-type semiconductor layer forming step)
Next, as illustrated in FIG. 2B, a P-type semiconductor layer 14 is formed over the first electrode 12 as a first semiconductor layer.
The P-type semiconductor layer has, for example, the general formula Si _n X _m (where X represents a hydrogen atom and / or a halogen atom, n represents an integer of 5 or more, and m represents an integer of n, 2n-2, or 2n. A boron-containing compound is added to a liquid silicon compound (especially a silane compound) having a ring system represented by the following formula. It can be formed using diluted and filtered liquid material. The solvent used here is not particularly limited as long as it dissolves the silane compound and / or the compound containing boron and does not react with the solute. Examples of the boron-containing compound used for forming the P-type semiconductor layer include diborane [B ₂ H ₆ ], tetraborane [B ₄ H ₁₀ ], and pentaborane [B _{5 in} addition to a silane compound containing a boron atom. H ₉ ], hexaborane [B ₆ H ₁₀ ], decaborane [B ₁₀ H ₁₄ ], trimethyl boron [B (CH ₃ ) ₃ ], triethyl boron [B (C ₂ H ₅ ) ₃ ], triphenyl boron [B ( C ₆ H ₅ ) 3] and the like.

  The liquid material described above can be applied on the first electrode 12 by using a spin coating method, a roll coating method, a curtain coating method, a dip coating method, a spray method, an ink jet method, etc. It is formed to about 10 nm. After application, baking is performed (for example, 400 ° C. for 1 hour) to form doped amorphous silicon. If necessary, crystallization is performed by laser irradiation or the like.

  As a specific example, 1 mg of decaborane and 1 g of cyclohexasilane are dissolved in 20 g of toluene to prepare a coating solution. This solution is spin-coated on a substrate 10 in an argon atmosphere and dried at 150 ° C., and then contains 3% hydrogen. A method of thermally decomposing at 450 ° C. in argon to form a P-type amorphous silicon film having a thickness of about 60 nm can be mentioned.

(Liquid repellent film forming process)
Subsequently, a liquid repellent film 15 is formed on the P-type semiconductor layer 14. The liquid repellent film can be obtained by first forming a liquid repellent monomolecular film on the entire surface of the P-type semiconductor layer 14 and then removing unnecessary portions. The liquid repellent film is, for example, a compound having a liquid repellent organic residue at one end and a functional group capable of binding to the substrate surface at the other end (for example, Y _n SiX _(4-n) [where Y Represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group; X represents an alkoxyl group or a halogen; n represents an integer of 1 to 3] Etc.) can be formed by contacting the surface of the substrate 10 and the amorphous silicon film 12.

  Alternatively, a monomolecular film made of fluorinated alkylsilane (FAS) is also preferable. In this case, for example, the FAS monomolecular film is formed on the entire surface of the substrate by placing the FAS 100 mg and the substrate in a sealed container and leaving the substrate at room temperature for 1 day, and then baking the substrate at 120 ° C. for 1 hour.

  Next, the liquid repellent monomolecular film formed in the region where the I-type semiconductor layer is to be formed is removed. This step can be performed, for example, by irradiating ultraviolet rays through a mask having an opening in a region where the liquid repellent monomolecular film is to be removed. In the case of FAS, the irradiated portion of FAS can be decomposed and removed by irradiating with ultraviolet rays having a wavelength of about 172 nm. FIG. 2C shows a state in which the liquid repellent film 15 is formed in a necessary region in this way.

  Here, in order to obtain a sufficient film thickness as the I-type semiconductor layer, the diameter of the droplet containing the silicon compound is preferably 100 μm to 600 μm, more preferably 200 μm to 400 μm. This size is preferable.

(Silicon film precursor film formation process)
Next, as shown in FIG. 2D, a liquid silicon material not containing a dopant source is ejected by an ink jet method, and a region where the liquid repellent film 15 of the P-type semiconductor layer 14 is not formed, that is, a lyophilic layer. A droplet is placed in the portion and dried to form a precursor film 16 ′ of a silicon film.

Examples of the liquid silicon material include a general formula Si _n X _m (where X represents a hydrogen atom and / or a halogen atom, n represents an integer of 5 or more, and m represents an integer of n, 2n-2, or 2n. A liquid silicon compound (especially a silane compound) having a ring system represented by UV is polymerized by irradiating with ultraviolet light, diluted with toluene solvent to about 10%, and passed through a filter. Can do.

  Here, FIG. 3 shows an example of a droplet discharge device (inkjet device) used in the inkjet method. 3 includes a mounting table 32 on which the substrate 10 is mounted, an x-axis driving roller 34 that moves the mounting table 32 in the x-axis direction (main scanning), and a liquid having a nozzle 36. It has a droplet discharge head 38 and a y-axis drive mechanism 40 that moves (sub-scans) the droplet discharge head 38 in the y-axis direction.

  A liquid silicon material is accommodated in the droplet discharge head 38 and is discharged as a droplet 42 from a small hole formed at the tip of the nozzle 36. The film is formed by moving the mounting table 32 in the x-axis direction and discharging the droplets 42 from the small holes of the nozzles 36 while reciprocating the droplet discharge head 38 in the y-axis direction. At this time, if the contact angle of the droplet containing the silicon compound with respect to the liquid repellent film 15 is between 40 degrees and 120 degrees, a thicker silicon film can be suitably formed.

(Heat treatment process)
Subsequently, as shown in FIG. 2E, baking is performed at 400 ° C. for 1 hour to convert the precursor film 16 ′ of the silicon film into an amorphous silicon film (I-type semiconductor layer) 16. At this time, the liquid repellent film 15 is decomposed and removed. When fired, the film thickness decreases, but according to the method of the present invention, the height of the droplet after the heat treatment is 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more.

  In the case of the heat treatment, an amorphous silicon film is generally obtained when the ultimate temperature is about 550 ° C. or lower, and a polycrystalline silicon film is obtained at higher temperatures. When it is desired to obtain an amorphous silicon film, it is preferably 300 ° C. to 550 ° C., more preferably 350 ° C. to 450 ° C. If the ultimate temperature is less than 300 ° C., the thermal decomposition of the silane compound does not proceed sufficiently, and a silicon film with sufficient characteristics may not be formed. The atmosphere in which the heat treatment is performed is preferably an atmosphere mixed with an inert gas such as nitrogen, helium or argon, or a reducing gas such as hydrogen. When it is desired to obtain a polycrystalline silicon film, the amorphous silicon film obtained above can be converted into a polycrystalline silicon film by irradiating a laser. The atmosphere in which the laser is irradiated is preferably an atmosphere that does not contain oxygen, such as an inert gas such as nitrogen, helium, or argon, or a mixture of these inert gases with a reducing gas such as hydrogen. Note that a polycrystalline silicon film can be obtained by irradiating a laser such as an excimer laser instead of the heat treatment. Alternatively, the amorphous silicon film may be obtained by firing and then crystallized by laser irradiation.

(Insulating film formation process)
Next, as shown in FIG. 2F, the gap between the island-shaped I-type semiconductor layers 16 is filled with an insulating film 17. The type of the insulating film 17 is not particularly limited, and an SiO ₂ film or the like can be used. As a forming method, a general sputtering method, a CVD method, or the like can be used. A feature of the method for manufacturing a photoelectric conversion element according to the present invention is that a vacuum process is not required and an I-type semiconductor layer is formed using a liquid material, so that other thin films are also unified with a method using a liquid material. Thus, all processes can be performed under the same apparatus and environment. Therefore, the insulating film 17 can be formed, for example, by applying polysilazane only to a region between the islands by an ink jet method and baking it in the atmosphere to form a SiO ₂ film. Or you may apply | coat the liquid containing the silicon compound mentioned above, and may bake in air | atmosphere.

  The insulating film 17 can prevent the P-type semiconductor layer 14 from joining to an N-type semiconductor layer that will be formed later.

(N-type semiconductor layer and second electrode forming step)
Next, as shown in FIG. 2G, the N-type semiconductor layer 18 and the second electrode 20 are formed. The N-type semiconductor layer 18 can be formed by using a compound containing phosphorus in place of the compound containing boron in the method for forming the P-type semiconductor layer 14 described above. Examples of such phosphorus-containing compounds include, in addition to modified silane compounds containing phosphorus, phosphine [PH ₃ ], diphosphine [P ₂ H ₄ ], trimethylphosphine [P (CH ₃ ) ₃ ], triethylphosphine. [P (C ₂ H ₅ ) ₃ ], triphenylphosphine [P (C ₆ H ₅ ) ₃ ], yellow phosphorus [P ₄ ] and the like can be mentioned.

  Specifically, 1 mg of yellow phosphorus and 1 g of cyclopentasilane are dissolved in a mixed solvent of 10 g of toluene and 10 g of decalin to prepare a coating solution, spin-coated in an argon atmosphere, dried at 150 ° C., and then argon containing 3% hydrogen If thermal decomposition is performed at 450 ° C., the N-type semiconductor layer 18 having a thickness of about 60 nm can be formed.

  Finally, a liquid material of an organic compound containing indium and tin is applied, and heat treatment is performed to convert the material into an ITO film, thereby forming the second electrode 20.

<Second Embodiment>
In this embodiment, after forming an island-shaped silicon film as the I-type semiconductor layer, a thicker I-type semiconductor layer is formed by disposing a droplet having a silicon compound offset from the already formed silicon film. It is characterized by forming.

  Silicon which is an I-type semiconductor layer in an island shape by performing a first electrode forming step, a P-type semiconductor layer forming step, a liquid repellent film forming step, a silicon film precursor film forming step, and a heat treatment step A film is formed. FIG. 4A shows a plan view of a part of the state where an island-like silicon film is formed, and FIG. 5A shows a cross-sectional view taken along the line VA-VA in FIG.

(Liquid repellent film forming process: second time)
Subsequently, as shown in FIG. 4B and FIG. 5B which is a cross-sectional view taken along the line VB-VB of the same figure, the P-type semiconductor layer 14 and the I-type semiconductor layer 16 are entirely covered. Then, the liquid repellent film 50 is formed. Since the method of forming the liquid repellent film is as described above, the description thereof is omitted here.

(I-type semiconductor layer formation process: second time)
Next, in the apparatus of FIG. 3, the droplet discharge head 38 and the table 32 are slightly shifted from the position where the precursor film of the I-type semiconductor layer 16 is formed in a lattice shape, and droplets containing a silicon compound are discharged and arranged. To do. FIG. 4C shows a state in which the silicon film precursor film 52 ′ is formed by drying after the arrangement. Since it is disposed on the liquid repellent film 50, a precursor film having a film thickness on the order of microns can be formed by the surface tension of the droplet. A cross-sectional view taken along line VC-VC in FIG. 4C is shown in FIG.

  Subsequently, as shown in FIG. 4D, a heating process or a light irradiation process is performed to form an I-type silicon film 52. A heating process and a light irradiation process can be performed similarly to the method in 1st Embodiment. The liquid repellent film is decomposed and removed by the heat treatment, so that the I-type silicon films 16 and 52 function as one body. FIG. 4D shows a plan view of this state, and FIG. 5D shows a cross-sectional view taken along the line VD-VD of FIG. 4D.

(Liquid repellent film formation step and I-type semiconductor layer formation: third time)
Further, a liquid repellent film is formed so as to cover the whole again. Since this is the same as the second liquid-repellent film forming step, description thereof is omitted. Thereafter, the droplet discharge head 38 and the table 32 are further shifted slightly, and droplets containing a silicon compound are discharged and arranged in the same manner as in the second step of forming the I-type semiconductor layer. After the placement, the silicon film precursor is dried to form a precursor, and the precursor film is integrated with the previously formed I-type silicon film through the heating process and the light irradiation process, as in the second time. This state is shown in FIG.

(Liquid repellent film formation step and I-type semiconductor layer formation: fourth time)
Again, a liquid repellent film is formed so as to cover the whole as in the third time. As in the third time, the head and the table are slightly shifted, and ejection, drying, heating and light irradiation are performed to form an I-type silicon film integrated with the I-type silicon film formed so far. This state is shown in FIG. Thus, according to this embodiment, a sufficiently thick I-type semiconductor layer suitable for a solar cell can be formed on the entire surface of the P-type semiconductor layer 14 by a method using a liquid material. Further, by repeatedly forming the silicon film repeatedly, a thicker I-type semiconductor layer can be manufactured in a simple process.

  After forming the silicon film, the N-type semiconductor layer and the second electrode are formed according to the method described in the first embodiment, and the photoelectric conversion element 1 is manufactured.

(Electronics)
The electronic device of the present invention includes such a photoelectric conversion element 1. Hereinafter, the electronic apparatus of the present invention will be described with reference to FIGS.

  FIG. 6 is a plan view showing a calculator to which the electronic device of the present invention is applied, and FIG. 7 is a perspective view showing a mobile phone (including PHS) to which the electronic device of the present invention is applied. A calculator 100 illustrated in FIG. 6 includes a main body 101, a display unit 102 provided on the upper surface (front surface) of the main body 101, a plurality of operation buttons 103, and a photoelectric conversion element installation unit 104. In the configuration shown in FIG. 6, five photoelectric conversion elements 1 are arranged in series in the photoelectric conversion element installation unit 104.

  A cellular phone 200 illustrated in FIG. 7 includes a main body portion 201, a display portion 202 provided on the front surface of the main body portion 201, a plurality of operation buttons 203, an earpiece 204, a mouthpiece 205, and a photoelectric conversion element installation portion 206. I have. In the configuration illustrated in FIG. 7, the photoelectric conversion element installation unit 206 is provided so as to surround the display unit 202, and a plurality of photoelectric conversion elements 1 are arranged in series. Note that the electronic device of the present invention can be applied to, for example, an optical sensor, an optical switch, an electronic notebook, an electronic dictionary, a wristwatch, a clock, and the like in addition to the calculator shown in FIG. 6 and the cellular phone shown in FIG.

  As mentioned above, although illustrated each embodiment about the manufacturing method of the photoelectric conversion element of this invention, a photoelectric conversion element, and an electronic device, this invention is not limited to these, The structure of each part is the same function. It can be replaced with any configuration that exhibits In addition, in the photoelectric conversion element of the present invention, other configurations (for example, one or more layers for any purpose) may be added between the layers.

It is a perspective view which shows 1st Embodiment of the photoelectric conversion element which concerns on this invention. It is explanatory drawing which shows the manufacturing process of the photoelectric conversion element which concerns on this invention. 1 shows a droplet discharge device used in a method for manufacturing a photoelectric conversion element according to the present invention. It is explanatory drawing which shows 2nd Embodiment of the photoelectric conversion element which concerns on this invention. It is sectional drawing along the VA-VA line-VD-VD line | wire of FIG. 1 illustrates an example of an electronic apparatus according to the invention. 1 illustrates an example of an electronic apparatus according to the invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Substrate, 12 ... First electrode, 14 ... First semiconductor layer, 15, 50 ... Liquid repellent film, 16, 52 ... I-type semiconductor layer, 16 ', 52' ... I-type semiconductor layer Precursor film, 17 ... insulating film, 18 ... second semiconductor layer, 20 ... second electrode, 30 ... droplet discharge device, 100 ... electronic device (calculator), 200 ... electronic device (mobile phone)

Claims (6)

Forming a first electrode on a substrate;
Forming a first conductivity type semiconductor layer on the first electrode;
Forming an I-type semiconductor layer on the first conductive semiconductor layer;
Forming a second conductivity type semiconductor layer different from the first conductivity type on the I type semiconductor layer;
Forming a second electrode on the second conductivity type semiconductor layer,
Forming the I-type semiconductor layer comprises:
Forming a precursor film of the I-type semiconductor layer by disposing droplets containing a silicon compound in an island shape on the first conductive semiconductor layer;
Performing a heat treatment or a light irradiation treatment on the precursor film to convert the precursor film into the I-type semiconductor layer;
Placing a droplet containing the silicon compound in a region where the I-type semiconductor layer arranged in the island shape on the first conductive type semiconductor layer is not formed. Method. Forming a film by arranging droplets containing a silicon compound in an island shape on a first conductive type semiconductor layer on a substrate;
Converting the film into an I-type semiconductor layer;
Disposing a droplet containing the silicon compound in a region where the I-type semiconductor layer disposed in the island shape on the first conductive semiconductor layer is not formed;
Forming a second conductivity type semiconductor layer on the I-type semiconductor layer.   A step of forming a liquid repellent film in a region other than the region where the droplet containing the silicon compound is to be disposed in the first conductive type semiconductor layer before the step of disposing the droplet in an island shape; Furthermore, the manufacturing method of the photoelectric conversion element of Claim 1 or 2 characterized by the above-mentioned.   The method for producing a photoelectric conversion element according to claim 3, wherein a contact angle of the droplet containing the silicon compound with respect to the liquid repellent film is adjusted to be 40 to 120 degrees.   5. The method of manufacturing a photoelectric conversion element according to claim 1, wherein the thickness of the I-type semiconductor layer is 1 μm or more after the step of converting into the I-type semiconductor layer.   The method for producing a photoelectric conversion element according to claim 1, wherein the droplets containing the silicon compound are arranged by an ink jet method.

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